Process for preparing sanitizing compositions



' positions and more par'tio a equipment and utensils.

and the like, but the -extensive'cbminercial use. of such solutions has been hampered somewhatby their relatively high cost of production andby t e inherent corrosive a starting material,

i yellow elemental p o's' crude iodine in treated. with the solu to red phosphorus becau "tively more expensive reag action mixture does not reaction with iodine it undergoes a valence change-of 5.

52,943,014 Patented "June 28, 1960 '1 i Equally asin'iportant'as the'relative cost, however-As the fact that in the reaction as employed in accordance o with the present invention, one mole of phosphoric acid I i v i v f f is produced as a byproduct of the reaction-for each-mole Q S of phosphorus.employed,'thereby providing a highly desirable additional constituent 'within the final solutions, in that, my investigations demonstrate that phosphates produced by partial neutralization of phosphoric acid are superior to any other inhibitor known for resisting cor- "Alfred -o. ia aia,1 1sw nanny. assignor to 'Chilean Nitrate Sales .Corporation; New-York, N.Y., a corpofation of New York 1 described. :Thus, being nontoxic, phosphoric acidis particularly suitable as a component for iodine solutions used to' sanitize food handling utensils and equipment. Fur- *therm'ore; the phosphoric acid being a weak acid, it'servestericidal 1}- to bufier the iodine solution, assuring that soaps and remov d Pm other alkaline materials with which the solutions come a for -Pi ,ih contact during use will not render the solutions alkag fdbdlhail'dl'iflg line: Inthis connection, the pH of the solutions in usep must be kept below 7.0 in order to prevent loss of avai-l- 11111135 been P p ed heretofore to empl y q able iodine by conversion to iodide and iodate.

iodine solutions for sanitizing food handling equipment Ch e... 9 .16 514) hi v's i n were" ess for producing 'solutionsoi iodinels for use as' antiseptic's and in lSa'Ilitli phosphorus results in the formation of hydriodic acid (HI) which, because of its highly corrosive nature,is an 'undesir'able constituent of the solutions. While the hyactibn tendency of iodine Sclutidfi 0 attack metals- 'clriod'ic acid could be neutralized with caustic soda, this: The present invention contemplates t p io of isfiindesirab e because of the necessity for maintaining impro pr c s i PIQGllPiPE iodine SQ F P the a relatively low'pfi of the/final product. In accordance general Q 3 5 desc'fibfld, l f h yp gm crqd iuc i with the process of the invention, I effectively neutralize i the acid and am able to achieve important advantages by incorporating in the reaction mixture, after the iodine: and phosphorus have reacted, a material which will react with the hydriodic acid .to yield additional prosphoric acid and an iodide which is relatively less corrosive. In particular- I employ an alkali phosphate, preferably sodium phosphate, toreact with the hydriodic acid, yielding sodium iodide andphosphoric acid. Advantag eousl y -the primary or secondary sodium phosphates, or combi-- nations thereof, can be used. The sodium phosphate is 40 employed in stoichiometric proportions for reaction with'v the hydriodic acid, or in slight excess.

Depending upon the particular use to which the iodine solution is to be put, a pH lower than that which will- "normally be obtained in'ithereaction mixture may be desired. I prefer to adjust the pH of the solutions by the: simple expedient of incorporating additional phosphoric acid therein. Similarly, it is desirable to maintain a relatively low freezing point and to limit vaporization of the o solutions of the invention, and I may accomplish this 999lhifYP by incorporating in the final solution a relatively small i i i Proportionbf p py y l l snqwn @QQFQ Y 9 In carrying out reduction of the crude iodine by yellow yellow phosphorus to prom e viol entor u rollable reactions. on the other hand, red phosplioru ma 's-ins;ii"'i+2ii;i o. o I have also found "tliatfpliosph eiiiielleii't cariosion inhibitors for iod ine jsoluti r metal food han t and the like when While the use if has been proposed heretoforegiic temperature as hereinbefore explained and to. maintain han ye Ph PP w the limited temperature until all or the phosphorus has ha dats c i re di r been consumed. Alternatively, 1 ma rel on simple dl with Yellow P 49 n mi maj "visual observation to insure control of the reaction, in l 6011301 of h 3 'F PI Q dZ 'thq' a t e is that the reaction mixture is substantially colorless and one iiiifried o i an q ii u i i' l l 156 i061 $15 qd may readily detect any accumulation of solid iodine and r l h ha 7 phosphorus vvithin the reaction vessel. I then heat the reaction mixture to a temperature not exceedingabout rate otherwise controlled i C. with the addition of a small amount of iodine to appreciable quantities of pure phosp assure conversion of the lower oxidized forms of phoscontact with each other 1m phorus to their highest valence state. The additional yellow phosphorus is p p I with other available reduc p, weight basis, its use in the process of the p invent-ion actually results in a considerable'siavings incost by reason of its low atomic weight and the fact that-inf the amount of iodine may be 1-5 of the weight of the stoichionietric quantity. The solution is then cooled to about 40 0., alkali phosphate is added to neutralizethe HI, and additional iodine dissolved therein to give the desired proportion of titratable free iodine. The resulting solution thus 'cdrnprisestitratable tree iodine, iodide "and a proportion of partially neutralized phosphoric acid effective to butter the solution against alkalinity and to Accordingly, one pound of yellow phosphbilis will 'reduce 20 pounds of iodine to the iodide state.

It will be noted that thereduction of iodine with yellow phosphorus, I find it advantageous to limit the reaction inhibit corrosion of metals by the iodine during use of the solution in sanitizing metal utensils.

It is believed that the invention may be best understood by reference to the following specific examples of typical solutions, prepared by the principles outlined above:

- EXAMPLE I Yellow phosphorus (stick form), in amount 2.7 grams (0.0872 mol), was covered with 1 liter of water at room temperature. The stoichiometric quantity of crude iodine, 55.3 grams, for reaction with the phosphorus to elfect reduction of the iodine to iodide and oxidation of the phosphorus to phosphoric acid was added slowly while continually stirring the reaction mixture. When all of the phosphorus had been consumed and the addition of iodine was complete, the reaction mixture was heated to 70 C., and additional crude iodine added progressiv'ely until the color of free iodine persisted, the total additional iodine being 1.5 grams. This step insures complete conversion of any of the lower oxidized forms of phosphorus to its highest valence state as represented by phosphoric acid. The solution was then cooled to 40 C. and 40 grams additional iodine was dissolved therein to provide a stock solution containing by weight about 3.6 to 4% free, titratable iodine, 5 to 5.5% iodide ion, and 0.8 to 0.9% phosphoric acid.

While this solution is directly usable as a sanitizing agent, as was explained hereinbefore, it may be diluted and/or modified for particular applications by the addition of various reagents, such, for example, as wetting agents, humectants or suitable reagents for converting the hydriodic acid content to a less corrosive form. The

following formulations are typical of many which may be prepared from the stock iodine solution obtained above:

Formulation I Sodium dihydrogen phosphate, in amount of 25 grams,

and 36 grams of propylene glycol were dissolved in 500 milliliters of the stock solution and thereafter the solution was diluted to 1.0 liter with water. Ten milliliters of this formulation in 1 gallon of water yields approximately 50 parts per million of free iodine and a solution' pH of about 4.1.

The formulation was found to have the following composition:

Concentra- Constituents tion, Grams Per Liter 1 rec iodine. 19. 4 Iodide ion 26. 3 Phosphoric acid 25. 3 Propylene glycol 36. 3

Formulation Il Concentra- Gonstituents tion, Grams Per Liter Free iodine 19. 4 Iodide ion 26. 3 Phosphoric 7 V I .155. 3 Propylene gly 36.0

The bactericidal efficiency of several phosphoric acid iodide-iodine solutions prepared in accordance with the principles of the invention were tested in comparison with several commercially available so-called iodophors (iodo=iodine and phor=carrier), and other preparations of free iodine, against the microorganisms Salmonella typhosa and Micrococcus pyogenes var. aureus by test procedures recommended by the US. Department of Agriculture (The Manual of the A.0.A.C., 1955, 8th ed, Available Chlorine Germicidal Equivalent Concentration ()F-irst Action; also Ind. and Eng. Chem. 1953, 45, 1013-1015). Sodium hypochlorite solutions were employed in the tests as chlorine controls. The various preparations included within these tests are identifiable as follows:

Designation Nature of Preparation H 8.0). Sodium Hypochlorlte Control Solution (5.76 percent available chlorine diluted with distilled water).

" was added to 10 milliliter dilutions of a sanitizing solution (a ratio of 1 to 200) to be tested. One minute later, a 4 millimeter standard loopful of the bacteria-germicide mixture was transplanted to a sterile tube containing 10 milliliters broth. Thirty seconds later, another increment of the bacteria was added, and a minute later another 4 millimeter loopful was transplanted. This was repeated until ten (10) increments had been added and ten (10) loopfuls of the mixture transplanted. The transplants were then incubated at 37 C. for 48 hours and the absence or presence of growth was noted macroscopically.

The results of the tests are represented in tabulated form in the following table, wherein the numerical values designate the number of increments of test bacteria completely killed. Thus, with'reference to the table, it will be seen that 20 ppm. free iodine in the phosphoric acid iodide-iodine solutions and in the iodophor solutions at 20 C. killed through and including the tenth increment, whereas 50 p.p.m. free iodine at 20 C. were required for iodine solutions A and B to obtain similar results.

' Sodium hypochlorite solutions diluted with phosphate buffer to contain 200 p.p.m. chlorine were capable of killing at 20 C. up to and including only the seventh increment, and up to and including only the fourth increment when diluted with distilled water. The overall test results demonstrate that the solutions prepared by he process of the invention, designated E andF, possess germicidal efliciencies equal to those of the commercial iodophor solutions, C and D, and that they are considerably better than the standard iodine solutions, A and B, and far better than the hypochlorite solutions G and H. The results of even more drastic tests also demonstrating the high germicidal efliciencies of sanitizing solutions prepared bythe process of the invention, may be seen by reference to the report entitled, Iodine Sanitizing Solutions.by Louis Gershenfeld and Bernard Witlin, ap-

pearing in Soap and Chemical Specialties, 31, 189 (Dec. 1955).

TABLE Germicidal capacity tests [10 ml. germ1clde+0.05 ml. lnoculum] Bacteria T3131) p.p.m. A B G D E F G H 2 1 1 2 2 2 2 0 4 l 1 4 4 4 4 O 0 6 1 1 5 5 5 0 0 8 1 l 5 5 5 5 O O 20 3 3 6 6 6 6 0 O 20 4 4 10 10 10 10 O 0 25 5 5 l0 10 10 10 0 0 50 10 10 l0 l0 10 10 2 0 23 i2 i8 i8 i8 it as 2 2 2 1 1 2 2 2 2 0 o 4 l 1 4 4 4 4 0 0 6 l 1 5 5 5 5 0 0 8 1 1 5 5 5 5 0 0 37 1O 3 8 6 6 6 6 0 0 20 4 4 10 10 10 10 0 0 25 5 5 10 10 10 10 0 0 50 10 l0 10 10 10 10 3 l 100 10 10 10 10 10 10 4 3 200 10 10 10 10 10 10 7 6 2 0 0 1 l 1 1 0 0 4 (l 0 1 l l 1 0 0 6 0 0 1 1 1 1 0 0 8 0 0 3 3 3 3 0 0 37 10 l l 6 6 6 6 O 0 2O 2 2 10 10 10 1O 0 0 25 3 3 10 1O 10 10 0 0 5O 5 5 l0 l0 10 10 2 0 100 10 10 10 10 10 10 3 Z M.Pyogenesvar. 8 g 2 g 3 0 4 o 0 1 1 1 1 0 o 6 0 0 2 2 2 2 0 0 8 0 0 4 4 4 4 0 0 2O 10 1 1 7 7 7 7 0 0 20 2 2 10 10 1O 10 0. 0 25 4 4 l0 10 10 10 0 0 50 5 5 10 10 10 10 2 0 100 10 10 10 10 10 10 4 3 200 10 10 10 10 l0 l0 7 6 Having thus described the subject matter of this invention, what it is desired to secure by Letters Patent is:

1. The method for preparing bactericidal solutions suitable for sanitizing food-handling equipment and the like that comprises, reacting crude iodine with yellow elemental phosphorus'i-n substantially stoichiometric proportions to effect reduction of the iodine to hydriodic acid and oxidation of the phosphorus to phosphoric acid, said reaction being effected by the controlled addition of the iodine to an aqueous reaction medium containing said phosphorus at a rate such that the temperature of the reaction mixture does not exceed about 55 C., and thereafter efiecting neutralization of the resulting hydriodic acid by the addition to the reaction mixture of sodium phosphate in a substantially stoichiometric quan-.

tity for reaction with the hydriodic acid to yield additiona1 phosphoric acid and sodium iodide.

2. The method for preparing bactericidal solutions suitable for sanitizing food-handling equipment and the like that comprises, reacting crude iodine with yellow elemental phosphorus in substantially stoichiometric proportions to effect reduction of the iodine to hydriodic acid and oxidation of the phosphorus to phosphoric acid, said reaction being effected by the controlled addition of the iodine to an aqueous reaction medium containing said phosphorus at a rate such that the temperature of the reaction mixture doesnot exceed about C., dissolving additional iodine within the resulting solution to provide a desired proportion of titratable free'iodine therein, thereafter adding sodium phosphate to said reaction mixture in a substantially stoichiometric quantity for reaction with the hydriodic acid to yield additional phosphoric acid and sodium iodide, and recovering a final solution containing titratable free iodine, sodium iodide and partially neutralized phosphoric acid in an amount suflicient to buffer the solution and to inhibit corrosion of metals by the iodine when said solution is employed for sanitizing purposes.

*3. The method as claimed in claim 1, wherein the sodium phosphate is primary sodium phosphate.

4. The method as claimed in claim 1, wherein the s0- dium phosphate is secondary sodium phosphate.

5. The method for preparing bactericidal solutions suitable for sanitizing food-handling equipment and the like that comprises, reacting crude iodine and yellow elemental phosphorus in substantially stoichiometric proportions to effect reduction of the iodine to hydriodic acid and oxidation of the phosphorus'to phosphoric acid, said reaction being efiected by the controlled addition of the phosphorus to an aqueous reaction medium containing said iodine at a rate such that the temperature of the reaction mixture does not exceed about 55 C., dissolving additional iodine within the resulting solution to provide a desired proportion of titratable free iodine therein, thereafter adding sodium phosphate to said reaction mixture in a substantially stoichiometric quantity for reaction with the hydriodic acid to yield additional phosphoric acid and sodium iodide, and recovering a final solution containing titratable free iodine, sodium iodide and partially neutralized phosphoric acid in an amount suflicent to buffer the solution and to inhibit corrosion of metals by the iodine when said solution is employed for sanitizing purposes.

References Cited the file of this patent V C. A. Jacobson: Encycl. of Chem. Reactions, Reinhold Press, 1948, p. 699. I

Mellor: Comprehensive Treatise on Inorg. and Theoretical Chem, Longman, Green and ('30., vol. 11, L922, pp. 171 and 596. 

5. THE METHOD FOR PREPARING BACTERICIDAL SOLUTIONS SUITABLE FOR SANITIZING FOOD-HANDLING EQUIPMENT AND THE LIKE THAT COMPRISES, REACTING CRUDE IODINE AND YELLOW ELEMENTAL PHOSPHORUS IN SUBSTANTIALLY STOICHIOMETRIC PROPORTIONS TO EFFECT REDUCTION OF THE IODINE TO HYDRIODIC, ACID AND OXIDATION OF THE PHOSPHORUS TO PHOSPHORIC ACID, SAID REACTION BEING EFFECTED BY THE CONTROLLED ADDITION OF THE PHOSPHORUS TO AN AQUEOUS REACTION MEDIUM CONTAINING SAID IODINE AT A RATE SUCH THAT THE TEMPERATURE OF THE REACTION MIXTURE DOES NOT EXCEED ABOUT 55*C., DISSOLVING ADDITIONAL IODINE WITHIN THE THE RESULTING SOLUTION TO PROVIDE A DESIRED PROPORTION OF TITRATABLE FREE IODINE THEREIN, THEREAFTER ADDING SODIUM PHOSPHATE TO SAID REACTION MIXTURE IN A SUBSTANTIALLY STIOCHIOMETRIC QUANTITY FOR REACTION WITH THE HYDRIODIC ACID TO YIELD ADDITIONAL PHOSPHORIC ACID AND SODIUM IODIDE, AND RECOVERING A FINAL SOLUTION CONTAINING TITRATABLE FREE IODINE, SODIUM IODIDE AND PARTIALLY NEUTRALIZED PHOSPHORIC ACID IN AN AMOUNT SUFFICENT TO BUFFER THE SOLUTION AND TO INHIBIT CORROSION OF METALS BY THE OIDINE WHEN SAID SOLUTION IS EMPLOYED TO SANITIZING PURPOSES. 